WO2012036185A1 - Metal complex, alteration product thereof, and compound useful in same - Google Patents

Abstract

This compound comprises a residue of the compound represented by formula (1) and a divalent aromatic group, there are 2 to 4 of the residue, there are 1-3 of the divalent aromatic group, and the sum of the number of the residue and the divalent aromatic group is 3-5. [In formula (1), Y¹-Y⁴ represent one of the groups represented in formula (2). In formula (2): R^α represents a hydrogen atom or a hydrocarbyl group; P¹-P⁴ are each a group of atoms forming a heterocycle containing Y¹-Y⁴; P⁵ and P⁶ are a group of atoms forming an aromatic ring or a heterocycle; Q¹ and Q² represent a linking group or a direct bond; and Z¹ and Z² represent a hydrogen atom or one of the groups represented in formula (3). In formula (3), R^β represents a hydrogen atom or a hydrocarbyl group.]

Description

Metal complexes, modified products thereof, and compounds useful therefor

The present invention relates to a metal complex, a modified product thereof, and a compound useful for the metal complex.
This application claims priority based on Japanese Patent Application No. 2010-209067 filed in Japan on September 17, 2010, the contents of which are incorporated herein by reference.

Metal complexes are known to be useful for electrode catalysts for fuel cells. As an electrode catalyst for a fuel cell, a metal complex consisting of a ligand composed of one macrocyclic compound or a ligand having a residue of one macrocyclic compound and a metal atom is used as a conductive carbon. A supported electrode catalyst is known (Patent Document 1).

JP 2009-173627 A

However, this electrode catalyst had insufficient oxygen reducing ability.

Therefore, an object of the present invention is to provide an electrode catalyst having a high oxygen reducing ability, a metal complex and a compound useful for the production thereof.

The first aspect of the present invention is:
A compound comprising a residue of a compound represented by the following formula (1) and a divalent aromatic group which may have a substituent, wherein the number of the residues is 2 to 4 And a compound in which the number of the divalent aromatic group is 1 to 3, and the sum of the number of the residue and the divalent aromatic group is 3 to 5.

[In Formula (1), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a group represented by any of the following formulas:

(In the formula, each R ^α independently represents a hydrogen atom or a hydrocarbyl group.)
P ¹ is an atomic group forming a heterocyclic ring containing Y ¹ ; P ² is an atomic group forming a heterocyclic ring containing Y ² ; P ³ forms a heterocyclic ring containing Y ³ ; P ⁴ is an atomic group forming a heterocyclic ring containing Y ⁴ ; P ⁵ and P ⁶ are each independently an atomic group forming an aromatic ring or a heterocyclic ring; P ¹ , The heterocyclic ring formed by P ² , P ³ and P ⁴ , and the aromatic ring and heterocyclic ring formed by P ⁵ and P ⁶ may each have a substituent; P ¹ and P ² are bonded to each other May form a ring with Q ¹ ; P ² and P ⁶ may be bonded to each other to form a ring; P ⁶ and P ⁴ may be bonded to each other to form a ring well; P ⁴ and P ³ may form a ring together with Q ² to combine with each other; may be the P ³ and P ⁵ are bonded to each other to form a ring; P ⁵ and P ¹ are each other It may bond to form a ring; Q ¹ and Q ² each independently a linking group or a direct bond; Z ¹ and Z ² are, each independently, a hydrogen atom, or, the following formula Represents a group represented by:

(In the formula, each R ^β independently represents a hydrogen atom or a hydrocarbyl group.)]

According to a second aspect of the present invention, in the first aspect, in the formula (1), an atomic group represented by P ⁵ and Z ¹ are combined to form a phenol structure, and P ^A compound in which an atomic group represented by ⁶ and Z ² are combined to form a phenol structure.

According to a third aspect of the present invention, in the first or second aspect, in the formula (1), a heterocyclic ring formed by P ¹ , a heterocyclic ring formed by P ² , a heterocyclic ring formed by P ³ , And the heterocycle formed by P ⁴ is an aromatic heterocycle.

According to a fourth aspect of the present invention, in the third aspect, in the formula (1), an aromatic heterocycle formed by P ¹ , an aromatic heterocycle formed by P ² , and an aromatic formed by P ³ A compound in which the heterocyclic ring and the aromatic heterocyclic ring formed by P ⁴ are nitrogen-containing aromatic heterocyclic rings.

In a fifth aspect of the present invention, the compound represented by the formula (1) in the first aspect is a compound represented by the following formula (2).

[In the formula (2), R ¹ is a hydrogen atom or a monovalent group; a plurality of R ¹ may be the same or different, and R ¹ are bonded to each other to form a ring. Q ³ and Q ⁴ each independently represent a divalent group represented by any of the following formulae:

[Wherein R ² represents a hydrogen atom or a monovalent group; a plurality of R ² may be the same or different, and R ² may be bonded to each other to form a ring; X ¹ represents a nitrogen atom or a trivalent group; R ³ represents a hydrogen atom or a monovalent group; a plurality of R ³ may be the same or different, and R ³ are bonded to each other. X ² may represent a group represented by any of the following formulas:

(Wherein R ′ represents a hydrogen atom or a hydrocarbyl group); a plurality of X ² may be the same or different; R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom; or represents a monovalent group; R ⁴ and R ⁶ may bond to each other to form a ring, R ⁵ and R ⁶ may bond to each other to form a ring, R ⁴ and R ⁵ and R ⁶ may combine with each other to form a ring. ]. ]

In a sixth aspect of the present invention, the compound in the first aspect is a compound represented by the following formula (3).

[In formula (3), R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent group; a plurality of R ⁷ may be the same or different, and R ⁷ may be mutually different. A plurality of R ⁸ may be the same or different, and R ⁸ may be bonded to each other to form a ring; Q ⁵ is a group represented by the following formula: Represents a divalent group represented by:

[Wherein R ⁹ represents a hydrogen atom or a monovalent group; a plurality of R ⁹ may be the same or different, and R ⁹ may be bonded to each other to form a ring. ; X ³ represents a nitrogen atom or a trivalent group; R ¹⁰ represents a hydrogen atom or a monovalent group; plural R ¹⁰ may be different even in the same, R ¹⁰ together are They may combine with each other to form a ring; X ⁴ represents a group represented by any of the following formulae:

(Wherein R ′ represents a hydrogen atom or a hydrocarbyl group);
A plurality of X ⁴ may be the same or different; R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent group, and R ¹¹ and R ¹² are bonded to each other. A ring may be formed. ];
Plural Q ⁵ may be the same or different; Ar represents a divalent aromatic group which may have a substituent. ]

A seventh aspect of the present invention is a metal complex having a metal atom or metal ion and a ligand, wherein the ligand is the compound according to any one of the first to sixth aspects. Is a metal complex.

The eighth aspect of the present invention is the metal complex according to the seventh aspect, wherein the metal in the metal atom or metal ion is a transition metal belonging to the fourth to sixth periods of the periodic table.

A ninth aspect of the present invention is the metal complex according to the eighth aspect, wherein the metal in the metal atom or metal ion is manganese, iron, cobalt, nickel, copper, or platinum.

A tenth aspect of the present invention is the metal complex according to any one of the seventh to ninth aspects, wherein the number of the metal atoms or the metal ions is 1 to 4.

The eleventh aspect of the present invention is a modified product obtained by heating a mixture comprising the metal complex according to any one of the seventh to tenth aspects and a carbon support.

The twelfth aspect of the present invention is the modified product according to the eleventh aspect, wherein the heating temperature is 600 ° C. to 1200 ° C.

According to a thirteenth aspect of the present invention, there is provided at least one selected from the group consisting of (a) the metal complex according to any one of the seventh to tenth aspects, and (b) a carbon support and a polymer compound. Composition containing components (hereinafter sometimes referred to as first composition). >.

A fourteenth aspect of the present invention is a composition comprising (a ′) the modified product in the eleventh or twelfth aspect and (b ′) a polymer compound (hereinafter, sometimes referred to as a second composition). . >.

A fifteenth aspect of the present invention is the metal complex according to any one of the seventh to tenth aspects, the modified product according to the eleventh or twelfth aspect, or the composition according to the thirteenth or fourteenth aspect. The catalyst which consists of these.

The sixteenth aspect of the present invention is a fuel cell electrode catalyst comprising the catalyst according to the fifteenth aspect.

The fuel cell electrode catalyst of the present invention has a high oxygen reducing ability. Moreover, this electrode catalyst for fuel cells can be easily manufactured by applying the metal complex and compound of this invention.

Hereinafter, the compound of the present invention will be described.

The compound of the present invention is a compound comprising a residue of the compound represented by the formula (1) and a divalent aromatic group which may have a substituent, and the number of the residues Is a compound in which the number of the divalent aromatic group is 1 to 3, and the sum of the number of the residue and the divalent aromatic group is 3 to 5. . The residue of the compound represented by the formula (1) is a group consisting of an atomic group obtained by removing part or all of the hydrogen atoms in the compound represented by the formula (1). The residue comprising the compound represented by the formula (1) is preferably a monovalent to tetravalent group, and more preferably a monovalent residue.

In the compound of the present invention, the residue of the compound represented by the formula (1) is monovalent, the number of the residues is 2, and the number of divalent aromatic groups is 1. Is particularly preferred.

In the compound of the present invention, the binding mode between the residue of the compound represented by the formula (1) and the divalent aromatic group is schematically shown as follows, for example.
CAC
C-A-A-C
C-A-C-A-C
CCCACCC
(In the formula, C represents a residue of the compound represented by formula (1); A represents a divalent aromatic group which may have a substituent.)

In the formula (1), in Y ¹ , Y ² , Y ³ and Y ⁴ , examples of the hydrocarbyl group represented by R ^α include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, n -Butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, norbornyl, nonyl, cyclononyl, decyl, 3,7-dimethyloctyl, adamantyl, Examples thereof include linear saturated hydrocarbyl groups having 1 to 50 carbon atoms such as dodecyl group, cyclododecyl group, pentadecyl group, octadecyl group and docosyl group, and branched or cyclic saturated hydrocarbyl groups having 3 to 50 carbon atoms. Preferably a linear saturated hydrocarbyl group having 1 to 8 carbon atoms or a branched or cyclic saturated hydrocarbyl group having 3 to 8 carbon atoms. It is a carbyl group.

In the formula (1), P ¹ , P ² , P ³ and P ⁴ are preferably each independently two carbon atoms adjacent to each other of Y ¹ , Y ² , Y ³ or Y ^4. It is an atomic group necessary to form a heterocycle together. Note that “two adjacent carbon atoms” does not include carbon atoms that may be included in R ^α .

In the formula (1), examples of the heterocyclic ring formed by P ¹ , P ² , P ³ and P ⁴ include pyrrolidine ring, piperidine ring, morpholine ring, piperazine ring, tetrahydrofuran ring, phosphole ring, phosphabenzene. Ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, N-alkyl pyrrole ring, furan ring, thiophene ring, thiazole ring, imidazole ring, oxazole ring, benzimidazole ring, benzofuran ring, benzothiophene ring, isoquinoline ring, quinazoline Preferably a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a pyrrole ring, a furan ring, a thiophene ring, an N-alkylpyrrole ring, and an imidazole ring; more preferably, a pyridine ring, a pyrrole ring, It is an imidazole ring. Further, the heterocyclic ring formed by P ¹ , P ² , P ³ and P ⁴ is preferably an aromatic heterocyclic ring, more preferably a nitrogen-containing aromatic heterocyclic ring.

In the formula (1), P ⁵ and P ⁶ are each independently an atomic group necessary for forming an aromatic ring or a heterocyclic ring.

In the formula (1), the heterocyclic ring formed by P ⁵ and P ⁶ is the same heterocyclic ring as the heterocyclic ring that P ¹ , P ² , P ³ and P ⁴ can form.

In the formula (1), examples of the aromatic ring formed by P ⁵ and P ⁶ include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring is preferable.

In the formula (1), examples of the direct bond represented by Q ¹ and Q ² include a single bond or a double bond, and a single bond is preferable.

In the formula (1), examples of the linking group represented by Q ¹ and Q ² include a divalent group or a trivalent group. In the following formulas (1-a) to (1-g), Groups represented by the following formulas (1-a) to (1-d) are more preferred, and groups represented by the following formulas (1-a) or (1-b) are preferred. Further preferred.

(In the formula, R ^δ represents a hydrogen atom or a monovalent group; when a plurality of R ^δ are present, they may be the same or different.)

Here, examples of the monovalent group represented by R ^δ include a hydrocarbyl group which may have a substituent and a monovalent aromatic group which may have a substituent.

The hydrocarbyl groups are the same groups as hydrocarbyl group represented by R ^alpha.

Examples of the monovalent aromatic group include a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group.

Examples of the substituent of the hydrocarbyl group and the monovalent aromatic group include a methyl group, an ethyl group, a tert-butyl group, a phenyl group, a naphthyl group, a 1,9-anthryl group, a pyridyl group, and a 1,10-phenanthryl. Groups.

In the formula (1), when P ¹ and P ² are bonded to each other to form a ring with Q ¹ , or P ⁴ and P ³ are bonded to each other to form a ring with Q ² , The compound represented by 1) has, for example, the structures represented by the following formulas (2-a) to (2-o); preferably, the following formulas (2-a), (2-j) ) To (2-o); more preferably, it has a structure represented by the following formula (2-a).

(Wherein R represents a hydrogen atom or a hydrocarbyl group having 1 to 30 carbon atoms; two Rs may be the same or different.)

Here, examples of the hydrocarbyl group having 1 to 30 carbon atoms represented by R include the same groups as the hydrocarbyl group represented by R ^α , and a hydrocarbyl group having 1 to 8 carbon atoms is preferable.

The heterocyclic ring formed by P ¹ , P ² , P ³ and P ⁴ may have a substituent. Examples of the substituent include halogeno groups such as a fluoro group, a chloro group, a bromo group, and an iodo group; a hydroxy group; a carboxyl group; a mercapto group; a sulfonic acid group; a nitro group; a phosphonic acid group; and an alkyl group having 1 to 4 carbon atoms. A silyl group having: methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, norbornyl group, Linear, branched or cyclic having 1 to 50 carbon atoms in total, such as nonyl, cyclononyl, decyl, 3,7-dimethyloctyl, adamantyl, dodecyl, cyclododecyl, pentadecyl, octadecyl, docosyl A saturated hydrocarbyl group of: methoxy group, ethoxy group, propyloxy group, butoxy group, pentylo Straight chain, branched or cyclic alkoxy groups having 1 to 50 carbon atoms such as cis group, cyclohexyloxy group, norbornyloxy group, decyloxy group, dodecyloxy group; phenyl group, 4-methylphenyl group, 1- Examples thereof include monovalent aromatic groups having 6 to 60 carbon atoms such as naphthyl group, 2-naphthyl group and 9-anthryl group. The substituent is preferably a halogeno group, a mercapto group, a hydroxy group, a carboxyl group, a saturated hydrocarbyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 30 monovalent aromatic groups; more preferably, chloro group, bromo group, hydroxy group, carboxyl group, methyl group, ethyl group, tert-butyl group, cyclohexyl group, norbornyl group, adamantyl group, methoxy group Group, ethoxy group, and phenyl group.

In the group represented by Z ¹ and Z ² in the formula (1), the hydrocarbyl group represented by R ^β is the same group as the hydrocarbyl group represented by R ^α .

In the formula (1), the structure in which P ⁵ and Z ¹ are combined or the structure in which P ⁶ and Z ² are combined is a structure represented by the following formulas (3-a) to (3-t). More preferred are structures represented by the following formulas (3-a) to (3-h), and further preferred are structures represented by the following formulas (3-a) to (3-d). The structure represented by the formula (3-a) or (3-b) is particularly preferable.

(In the formula, R ^ε represents a hydrocarbyl group having 1 to 10 carbon atoms, and when a plurality of R ^ε are present, they may be the same or different.)

The aromatic ring and heterocyclic ring formed by P ⁵ and P ⁶ may have a substituent, and examples of the substituent include the same groups as the substituent that P ¹ may have. It is done.

As the compound represented by the formula (1), the atomic group represented by P ⁵ and Z ¹ are united to form a phenol structure, and the atomic group represented by P ⁶ and Z ² And a compound in which a phenolic structure is formed is preferable.

As such a compound, since a metal complex is stabilized, a compound represented by the following formula (2) is preferable.

[In the formula (2), R ¹ is a hydrogen atom or a monovalent group; a plurality of R ¹ may be the same or different, and R ¹ are bonded to each other to form a ring. Q ³ and Q ⁴ each independently represent a divalent group represented by any of the following formulae:

[Wherein R ² represents a hydrogen atom or a monovalent group; a plurality of R ² may be the same or different, and R ² may be bonded to each other to form a ring; X ¹ represents a nitrogen atom or a trivalent group; R ³ represents a hydrogen atom or a monovalent group; a plurality of R ³ may be the same or different, and R ³ are bonded to each other. To form a ring; X ² represents a group represented by any of the following formulae:

(In the formula, R ′ represents a hydrogen atom or a hydrocarbyl group.)
A plurality of X ² may be the same or different; R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a monovalent group; R ⁴ and R ⁶ are bonded to each other; R ⁵ and R ⁶ may be bonded to each other to form a ring, and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. ]. ]

In the formula (2), the monovalent group represented by R ^1, include the same groups as the monovalent group represented by R ^[delta].

In the formula (2), the divalent group represented by Q ³ and Q ⁴ is preferably a divalent group represented by the following formulas (4-a) to (4-j); Divalent groups represented by formulas (4-a), (4-b), (4-d), (4-e), (4-g) to (4-j) are more preferable; Divalent groups represented by formulas (4-a), (4-b), (4-d), (4-e), (4-h), and (4-j) are more preferable; Divalent groups represented by the formulas (4-a), (4-b), (4-d), and (4-e) are particularly preferable.

[The divalent group represented by the formulas (4-a) to (4-j) may have a substituent; the substituent may have the substituent that P ¹ may have. Is the same group. ]

In Q ³ and Q ⁴ , the monovalent group represented by R ² in the above formula is the same group as the group exemplified for R ^δ .

Regarding Q ³ and Q ⁴ , examples of the trivalent group represented by X ¹ in the above formula include a methine group and a methine group substituted with a hydrocarbyl group.

In Q ³ and Q ⁴ , the monovalent group represented by R ³ in the above formula is the same group as the group exemplified for R ^δ .

In Q ³ and Q ⁴ , the monovalent group represented by R ⁴ , R ⁵ and R ⁶ in the above formula is the same group as the group exemplified for R ^δ . R ⁴ and R ⁶ may be bonded to each other to form a ring, R ⁵ and R ⁶ may be bonded to each other to form a ring, and R ⁴ , R ⁵ and R ⁶ are bonded to each other to form a ring. May be formed.

Examples of the compound represented by the formula (2) include compounds represented by the following formulas (5-a) to (5-i), and the following formulas (5-a) to (5- Compounds represented by i) are preferred, compounds represented by the following formulas (5-a) to (5-d) are more preferred, and compounds represented by the following formulas (5-a) to (5-c) More preferred is a compound.

[The compounds represented by the formulas (5-a) to (5-i) may have a substituent, and the substituent is the same as the substituent which P ¹ may have. ]

The “divalent aromatic group” constituting the compound of the present invention means the remaining atomic group obtained by removing two hydrogen atoms from an aromatic ring which is a single ring or a condensed ring.

Examples of the divalent aromatic group constituting the compound of the present invention include 1,4-phenylene group, 2,7-triphenylene group, 1,5-naphthylene group, 2,6-naphthylene group, 1,5-anthrylene group. , 9,10-anthrylene group, 2,7-pyrenylene group, 2,7-phenanthrene group, 3,8-phenanthrolene group, etc. Since the resulting compound is stable in the air, 1,4-phenylene group, 1,5-naphthylene group, 2,6-naphthylene group, 1,5-anthrylene group, 9,10-anthrylene group, 9,10 An anthrylene group is preferred. The divalent aromatic group may have a substituent.

As the compound of the present invention, a compound represented by the following formula (3) is preferable because synthesis is easy.

[In formula (3), R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent group; a plurality of R ⁷ may be the same or different, and R ⁷ may be mutually different. A plurality of R ⁸ may be the same or different, and R ⁸ may be bonded to each other to form a ring; Q ⁵ is a group represented by the following formula: Represents a divalent group represented by:

[Wherein R ⁹ represents a hydrogen atom or a monovalent group; a plurality of R ⁹ may be the same or different, and R ⁹ may be bonded to each other to form a ring. ; X ³ represents a nitrogen atom or a trivalent group; R ¹⁰ represents a hydrogen atom or a monovalent group; plural R ¹⁰ may be different even in the same, R ¹⁰ together are They may combine with each other to form a ring; X ⁴ represents a group represented by any of the following formulae:

(In the formula, R ′ represents a hydrogen atom or a hydrocarbyl group.)
A plurality of X ⁴ may be the same or different; R ¹¹ and R ¹² each independently represents a hydrogen atom or a monovalent group; R ¹¹ and R ¹² are bonded to each other; To form a ring. A plurality of Q ⁵ may be the same or different; Ar represents a divalent aromatic group which may have a substituent. ]

In the formula (3), the monovalent group represented by R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is the same group as the monovalent group represented by R ^δ. Can be mentioned.

In the above formula for Q ⁵ , examples of the trivalent group represented by X ³ include a methine group and a methine group substituted with a hydrocarbyl group. Examples of the hydrocarbyl group, the same group and the hydrocarbyl group represented by R ^alpha.

In the formula (3), examples of the divalent aromatic group which may have a substituent represented by Ar include the same groups as described above.

In the formula (3), in the divalent group represented by Q ⁵ , the hydrocarbyl group represented by R ′ is the same group as the hydrocarbyl group represented by R ^α .

As the compound represented by the formula (3), compounds represented by the following formulas (I-1) to (I-11) are preferable, and in the following formulas (I-1) to (I-7) Compounds represented by the following formulas (I-1) to (I-4) are more preferred.

[The compounds represented by formulas (I-1) to (I-11) may have a substituent, and the substituent is the same group as the substituent that P ¹ may have. . ]

The compounds of the present invention are described in, for example, Tetrahedron. 1999, 55, 8377. As described in 1., an organometallic reactant is added to a heterocyclic compound and subjected to an oxidation reaction, a precursor is synthesized by a halogenation reaction, and then a cross-coupling reaction using a transition metal catalyst, followed by ring closure with an aldehyde. It can be synthesized by reacting. The compound of the present invention can also be synthesized by adding an aldehyde to a compound having a pyrrolyl group at the terminal and bonding the pyrrolyl group to a methylene group.

The synthesis method will be described using the compound represented by formula (3) as an example among the compounds of the present invention. The compound represented by the formula (3) is preferably synthesized by a reaction between a compound represented by the following formula (4) and an aldehyde represented by the following formula (5) (see the following reaction scheme). .

[Wherein R ⁷ , R ⁸ , Q ⁵ and Ar have the same meaning as described above. ]

The reaction can be performed by dissolving the raw material in an appropriate solvent and using an acid as a catalyst. Here, the acid itself may be used as the solvent.

Examples of the acid include organic acids such as acetic acid, propionic acid, and butanoic acid; boron trifluoride; boron trifluoride etherate; boron trichloride; boron tribromide; trifluoroacetic acid; trifluoromethanesulfonic acid; Toluene sulfonic acid is mentioned.

When the acid itself is used as a solvent, the organic acid is preferable as the acid.

Examples of the solvent include dichloromethane, chloroform, carbon tetrachloride, methanol, ethanol, and combinations thereof.

The temperature of the reaction is usually 0 ° C. to 250 ° C., preferably 0 ° C. to 200 ° C., particularly preferably 0 ° C. to 160 ° C.

The reaction time is usually 1 minute to 1 week, preferably 5 minutes to 100 hours, and particularly preferably 1 hour to 72 hours.

The reaction temperature and reaction time can be adjusted by a combination of acid and solvent.

In the above reaction, an oxidizing agent such as oxygen, p-chloranil, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, which is generally easily available, can be added.

Next, the metal complex of the present invention will be described.
The metal complex of this invention is a metal complex which has a metal atom or metal ion, and a ligand, Comprising: The said ligand is a metal complex which is the said compound.

In the metal complex of the present invention, the number of the metal atoms or metal ions is usually 1 to 4, and preferably 2 to 4.

In the metal complex of the present invention, the metal atom or metal ion is bonded (usually coordinated) to a heteroatom in the compound that is a ligand. Here, when the total number of the metal atoms and metal ions is two or more, the metal complex of the present invention connects one metal atom or metal ion and another metal atom or metal ion with a bridging ligand. It may be a cross-linked complex. Examples of the partial structure of the metal atom and the oxygen atom in the crosslinked complex in which the hetero atom is an oxygen atom and the total of two metal atoms and metal ions are given below.

(In the formula, M represents a metal atom or a metal ion, and two Ms may be the same or different.)

The metal in the metal atom or metal ion can be classified into a transition metal and a typical metal. In the present specification, the “transition metal” means an element having an incomplete d shell or f subshell.

Examples of the transition metal include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technesium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, and tantalum. , Tungsten, rhenium, osmium, iridium, platinum, gold, mercury.

Examples of typical metals include aluminum, gallium, germanium, indium, tin, antimony, thallium, lead, and bismuth.

Among these metals, the transition metal belonging to the 4th to 6th periods is preferable because the catalyst performance is good; titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, rhodium, Palladium, silver, tantalum, tungsten, rhenium, osmium, iridium, platinum, and gold are more preferable; manganese, iron, cobalt, nickel, copper, and platinum are more preferable; iron, cobalt, and copper are particularly preferable.

The metal complex of the present invention may have at least one component selected from the group consisting of neutral molecules and counter ions that electrically neutralize the metal complex.

Examples of the neutral molecule include molecules that solvate to form a solvated salt, and include compounds other than the compound (for example, the compound represented by the formula (3)). Specifically, Water, methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, 1,1-dimethylethanol, ethylene glycol, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl- 2-pyrrolidone, dimethyl sulfoxide, acetone, chloroform, acetonitrile, benzonitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4'-bipyridine, tetrahydrofuran, diethyl ether, dimethoxyethane, methyl ethyl ether 1,4-dioxane and the like. The neutral molecule is preferably water, methanol, ethanol, isopropyl alcohol, ethylene glycol, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, chloroform, acetonitrile, benzo Examples include nitrile, triethylamine, pyridine, pyrazine, diazabicyclo [2,2,2] octane, 4,4′-bipyridine, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane. In the metal complex of the present invention, only one neutral molecule may be present or two or more neutral molecules may be present.

When the metal complex is a complex ion, a cation or an anion that makes the metal complex electrically neutral is selected as a counter ion that forms a complex salt with the metal complex.
When the complex ion is positively charged, examples of the counter ion include fluoride ion, chloride ion, bromide ion, iodide ion, sulfide ion, oxide ion, hydroxide ion, hydride ion, Sulfite ion, phosphate ion, cyanide ion, acetate ion, carbonate ion, sulfate ion, nitrate ion, hydrogen carbonate ion, trifluoroacetate ion, thiocyanide ion, trifluoromethanesulfonate ion, acetylacetonate, tetrafluoroborate Ion, hexafluorophosphate ion, tetraphenylborate ion, etc .; preferably chloride ion, bromide ion, iodide ion, oxide ion, hydroxide ion, hydride ion, phosphate ion, cyanide Fluoride ion, acetate ion, carbonate ion, sulfate ion, nitrate ion , Acetylacetonate, a tetraphenyl borate ion. When a plurality of counter ions are present, they may be the same or different. Moreover, neutral molecules and ions may coexist.
When the complex ion is negatively charged, examples of the counter ion include alkali metal ion; alkaline earth metal ion; tetraalkylammonium ion such as tetra (n-butyl) ammonium ion and tetraethylammonium ion; tetraphenylphosphonium And tetraarylphosphonium ions such as ions; preferably lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, magnesium ions, calcium ions, strontium ions, barium ions, tetra (n-butyl) ammonium ions, Tetraethylammonium ion and tetraphenylphosphonium ion; more preferably tetra (n-butyl) ammonium ion, tetraethylammonium ion, Phenyl phosphonium ion; more preferably, tetra (n- butyl) ammonium ion, a tetraethylammonium ion.

Examples of the metal complex of the present invention include compounds represented by the following formulas (6-aa) to (6-ll), and specifically include the following formulas (6-a) to (6- and a compound represented by g).

[In the formulas (6-aa) to (6-ll), M represents a metal atom or a metal ion; a plurality of Ms may be the same or different; The substituent is the same group as the substituent which P ¹ may have; and as described above, these compounds are a group consisting of a counter ion and a neutral molecule. It may have at least one component selected from ]

[The compounds represented by the formulas (6-a) to (6-f) may have a substituent, and the substituent is the same group as the substituent that P ¹ may have. These compounds may have at least one component selected from the group consisting of a counter ion and a neutral molecule, as described above. ]

Next, a method for synthesizing the metal complex of the present invention will be described.
In the metal complex of the present invention, for example, after the compound of the present invention is organically synthesized, the resulting compound is a reagent for imparting a metal atom (hereinafter sometimes referred to as “metal imparting agent”). It is obtained by mixing with and reacting. The amount of the metal-imparting agent to be reacted may be adjusted according to the target metal complex, but it is usually preferable that the amount is excessive with respect to the ligand.

Examples of the metal-imparting agent include acetate, fluoride, chloride, bromide, iodide, sulfate, carbonate, nitrate, hydroxide, perchlorate, trifluoroacetate, trifluoromethane, and the like. Examples include sulfonic acid, tetrafluoroborate, hexafluorophosphate, and tetraphenylborate, with acetate being preferred. Examples of the acetate salt include cobalt acetate (II), iron acetate (II), manganese acetate (II), manganese acetate (III), nickel acetate (II), copper acetate (II), and zinc acetate (II). Cobalt (II) acetate, iron (II) acetate, copper (II) acetate are preferred.

The metal imparting agent may be a hydrate such as cobalt acetate (II) tetrahydrate, manganese acetate (II) tetrahydrate, manganese acetate (III) dihydrate, nickel acetate ( II) Tetrahydrate, copper acetate (II) monohydrate, zinc acetate (II) dihydrate.

The reaction is preferably performed in the presence of a solvent (that is, a reaction solvent).

Examples of the solvent include water, acetic acid, aqueous ammonia, methanol, ethanol, n-propanol, isopropyl alcohol, 2-methoxyethanol, 1-butanol, 1,1-dimethylethanol, ethylene glycol, diethyl ether, 1 , 2-dimethoxyethane, methyl ethyl ether, 1,4-dioxane, tetrahydrofuran, benzene, toluene, xylene, mesitylene, durene, decalin, dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, 1,2-dichlorobenzene, N, N Examples include '-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, acetone, acetonitrile, benzonitrile, triethylamine, and pyridine.

These solvents may be used alone or in combination of two or more, but a solvent in which the compound of the present invention and the metal-imparting agent are dissolved is preferable.

The temperature of the reaction is usually −10 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., particularly preferably 0 ° C. to 100 ° C.

The reaction time is usually 1 minute to 1 week, preferably 5 minutes to 24 hours, and particularly preferably 1 hour to 12 hours.

The reaction temperature and reaction time can be adjusted depending on the type of the compound and metal imparting agent of the present invention.

In order to isolate and purify the metal complex formed after the completion of the reaction from the reaction solution, known means such as a recrystallization method, a reprecipitation method, and a chromatography method can be used alone or in combination.

Depending on the type of the solvent, the generated metal complex may precipitate. The precipitated metal complex may be separated by filtration or the like, washed as necessary, or dried to remove the metal complex. It can be isolated and purified.

Next, the modified product of the present invention will be described.
The modified product of the present invention can be obtained by heating a mixture comprising the metal complex and a carbon support. Thus, the solubility in water can be further lowered by using the metal complex of the present invention as a modified product. In addition, as for a metal complex and a carbon support | carrier, all may be used individually by 1 type, or may use 2 or more types together.

Examples of the carbon carrier include carbon particles such as Norrit, Ketjen black, Vulcan, black pearl, and acetylene black; fullerenes such as C60 and C70; carbon nanotubes; carbon nanohorns; carbon fibers; Black, Vulcan, Acetylene Black, Carbon Nanotube, and Fullerene; More preferably, Ketjen Black, Vulcan, and Carbon Nanotube; More preferably, Ketjen Black and Vulcan.

In the mixture, the mixing ratio of the metal complex and the carbon support is such that the content of the metal complex is preferably 5 to 70% by mass with respect to the total mass of the metal complex and the carbon support, and 10 to 60% by mass. More preferably, the content is 15 to 50% by mass.

Before the heating, it is preferable to dry the mixture at a temperature of 15 ° C. to 200 ° C. for 6 hours or more as a pretreatment. A vacuum dryer or the like can be used for this pretreatment.

Examples of the atmosphere for performing the heating include hydrogen, helium, nitrogen, ammonia, oxygen, neon, argon, krypton, xenon, acetonitrile, and a mixed gas thereof; hydrogen, helium, nitrogen, ammonia, oxygen , Neon, argon, and a mixed gas thereof are preferable; hydrogen, nitrogen, ammonia, argon, and a mixed gas thereof are more preferable.

The lower limit of the heating temperature is usually 600 ° C., preferably 700 ° C., more preferably 800 ° C. The upper limit is usually 1200 ° C, preferably 1100 ° C, more preferably 1000 ° C.
That is, the heating temperature is usually 600 ° C. or higher and 1200 ° C. or lower; preferably 700 ° C. or higher and 1100 ° C. or lower; more preferably 800 ° C. or higher and 1000 ° C. or lower.

What is necessary is just to adjust the time of the said heating with the atmosphere, temperature, etc. at the time of performing the said heating.
In the heating step, the gas may be gradually raised from room temperature in a sealed state or aerated state, and the temperature may be lowered immediately after reaching the target temperature. After reaching the value, it is preferable to gradually heat the metal complex by maintaining the temperature because durability can be further improved. The time for maintaining the temperature is usually 10 minutes to 100 hours, preferably 30 minutes to 40 hours, more preferably 1 to 10 hours, and further preferably 1 to 3 hours.

The heating can be performed by an apparatus such as an oven, a furnace, or an IH hot plate.

In the heating, the mass reduction rate before and after heating (that is, the mass reduction rate of the modified product obtained after heating with respect to the mass of the mixture before heating) is preferably 5% or more, more preferably 10% or more, and particularly preferably. May be performed until it becomes 15% or more. Further, the upper limit of the mass reduction rate is preferably 50%, more preferably 40%, and particularly preferably 30%.
That is, the heating is performed so that the mass reduction rate before and after heating is preferably 5% or more and 50% or less; more preferably 10% or more and 40% or less; particularly preferably 15% or more and 30% or less. Good.

The modified product after heating has good stability when the carbon content is high. Therefore, the carbon content is preferably 40% by mass or more, more preferably 60% by mass or more, and particularly preferably 80% by mass. The heating is performed so as to achieve the above.
The upper limit of the carbon content is preferably 99% by mass, more preferably 97% by mass, and particularly preferably 95% by mass.
That is, in the heating, the carbon content of the modified product is preferably 40% by mass or more and 99% by mass or less; more preferably 60% by mass or more and 97% or less; particularly preferably 80% by mass or more and 95% or less. You can do so.

The metal complex and modified product of the present invention may be used alone as they are, or may be used as a composition in combination with other components. Here, examples of the other components include the carbon carrier and a polymer compound. The first composition of the present invention is a composition comprising the metal complex and at least one component selected from the group consisting of a carbon carrier and a polymer compound, preferably the metal complex and carbon A composition substantially comprising at least one component selected from the group consisting of a carrier and a polymer compound. The second composition of the present invention is a composition comprising the modified product and a polymer compound, preferably a composition substantially comprising the modified product and the polymer compound. Further, the first composition of the present invention and the second composition of the present invention (hereinafter, these may be collectively referred to as “the composition of the present invention”) are usually solids. In addition, in the composition of this invention, each component may be used individually by 1 type, respectively, or may use 2 or more types together.

In the first composition of the present invention, the content of the carbon support is usually 100 parts by mass to 10,000 parts by mass, preferably 200 parts by mass to 600 parts by mass with respect to 100 parts by mass of the metal complex of the present invention. Part.
In the first composition of the present invention, the content of the polymer compound is usually 50 parts by mass to 500 parts by mass, preferably 100 parts by mass to 300 parts by mass with respect to 100 parts by mass of the metal complex of the present invention. Part by mass.

In the second composition of the present invention, the content of the polymer compound is usually 10 parts by mass to 200 parts by mass, preferably 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the modified product of the present invention. Part by mass.

Examples of the polymer compound include Nafion (registered trademark), polyvinylidene fluoride, polyether ether ketone, polysulfone, polyether sulfone, poly (arylene ether), polyimide, polyphenylene sulfide, polyphenylquinoxalen, polyphenylene, and polyphenylene vinylene. , Polyfluorene, polyethylene, polypropylene, polybutadiene, polyisoprene, polyvinyl chloride, polystyrene, polyacrylonitrile, polybenzimidazole, polyaniline, polypyrrole, polythiophene, polypyridine, and compounds in which sulfonic acid groups are introduced into these polymers. preferable.

Next, the usefulness of the metal complex, modified product and composition of the present invention (hereinafter sometimes referred to as “the metal complex of the present invention”) will be described.

The metal complex of the present invention acts as a catalyst in a redox reaction involving electron transfer such as an oxygen addition reaction, an oxidative coupling reaction, a dehydrogenation reaction, a hydrogenation reaction, and an oxide decomposition reaction (that is, a redox catalyst). Besides being used for synthesis, it can also be used for applications such as additives, modifiers, batteries, sensor materials, and electroluminescent materials.

The metal complex or the like of the present invention is preferably used as a redox catalyst. Specifically, hydrogen peroxide decomposition catalyst, aromatic compound oxidation polymerization catalyst, exhaust gas / drainage purification catalyst, dye-sensitized solar cell A redox catalyst layer, a carbon dioxide reduction catalyst, a reformed hydrogen production catalyst, an oxygen sensor, and the like.

In particular, in a reaction involving water, a water-soluble metal complex or the like easily flows out, but the metal complex or the like of the present invention is hardly dissolved in water because it is connected, and as a result, the outflow is suppressed.

The metal complex of the present invention is also useful as a light emitting material for organic EL elements, organic semiconductor materials such as organic transistors and dye-sensitized solar cells.

Hereinafter, the present invention will be described based on examples.

<Example 1>
Synthesis of compound (A)

(In the formula, Me represents a methyl group, and Boc represents a tert-butoxycarbonyl group.)

3.945 g 2,9-bis (3′-bromo-5′-tert-butyl-2′-methoxyphenyl) -1,10-phenanthroline, 3.165 g 1-N-Boc-pyrrole under argon atmosphere -2-boronic acid, 0.138 g of tris (benzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ), 0.247 g of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, and 5.527 g Of potassium phosphate was dissolved in a mixed solvent of 200 mL of dioxane and 20 mL of water and stirred at 60 ° C. for 6 hours. After completion of the reaction, the reaction solution was allowed to cool, and distilled water and chloroform were added to extract the organic layer. When the obtained organic layer was concentrated, a black residue was obtained. The residue was purified using a silica gel column to obtain compound (A).

The instrumental analysis result of the obtained compound (A) was as follows.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) = 1.34 (s, 18H), 1.37 (s, 18H), 3.30 (s, 6H), 6.21 (m, 2H) , 6.27 (m, 2H), 7.37 (m, 2H), 7.41 (s, 2H), 7.82 (s, 2H), 8.00 (s, 2H), 8.19 ( d, J = 8.6 Hz, 2H), 8.27 (d, J = 8.6 Hz, 2H).

・ Synthesis of compound (B)

Under a nitrogen atmosphere, 0.904 g of compound (A) was dissolved in 10 mL of dichloromethane. While the dichloromethane solution was cooled to −78 ° C., 8.8 mL of boron tribromide (1.0 M dichloromethane solution) was slowly added dropwise. After the dropwise addition, the solution was stirred as it was for 10 minutes and then allowed to stand while stirring until it reached room temperature. After 3 hours, the reaction solution was cooled to 0 ° C., saturated aqueous sodium hydrogen carbonate solution was added, chloroform was added for extraction, and the organic layer was concentrated to obtain a brown residue. The residue was purified by a silica gel column to obtain compound (B).

The instrumental analysis result of the obtained compound (B) was as follows.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) = 1.40 (s, 18H), 6.25 (m, 2H), 6.44 (m, 2H), 6.74 (m, 2H) 7.84 (s, 2H), 7.89 (s, 2H), 7.92 (s, 2H), 8.35 (d, J = 8.4 Hz, 2H), 8.46 (d, J = 8.4 Hz, 2H), 10.61 (s, 2H), 15.88 (s, 2H).

-Synthesis of compound (C)

Under a nitrogen atmosphere, 0.121 g of compound (B) and 0.013 g of terephthalaldehyde were dissolved in 30 mL of dichloromethane. To this, 1 drop of trifluoroacetic acid was added, followed by stirring at room temperature for 24 hours. Thereafter, 0.050 g of chloranil was added and stirred for 24 hours. Thereafter, the black residue obtained by concentrating the reaction solution was washed with chloroform and methanol in this order to obtain a compound (C).

The instrumental analysis result of the obtained compound (C) was as follows.
ESI-MS [M + H] ⁺ : 1307.5

<Example 2>
(Synthesis of metal complex (D))

In a nitrogen atmosphere, a mixed solution of 3 mL of methanol and 3 mL of chloroform containing 0.047 g of compound (C) and 0.018 g of cobalt acetate tetrahydrate was stirred for 5 hours while heating to 80 ° C. did. When the obtained solution was concentrated and dried to solidify, a green solid was obtained. This was washed with water to obtain a metal complex (D).

The instrumental analysis result of the obtained compound (D) was as follows.
ESI-MS [M-2 (CH ₃ COO)] ²⁺ : 768.2

<Example 3>
(Preparation of composition (E))
A metal complex (D) and a carbon support (Ketjen Black EC600JD, manufactured by Lion) were mixed at a mass ratio of 1: 4, and the resulting mixture was stirred in methanol at room temperature, and then 200 Pa at room temperature. A composition (E) was prepared by drying for 12 hours under reduced pressure.

<Example 4>
(Preparation of modified product (F))
The composition (E) was heated for 2 hours at 800 ° C. in a nitrogen atmosphere using a tubular furnace to obtain a modified product (F). Table 1 shows the mass reduction rate before and after heating and the carbon content of the modified product (F). The tubular furnace used for heating and the heating conditions are shown below.

Tubular furnace: Program-controlled open / close tubular furnace EPKRO-14R, Isuzu Seisakusho Heating conditions Atmosphere: Nitrogen gas flow (200 ml / min)
Temperature increase rate and temperature decrease rate: 200 ° C./hour

<Comparative Example 1>

Under a nitrogen atmosphere, 0.061 g of compound (B) and 0.012 g of benzaldehyde were dissolved in 5 mL of propionic acid and heated at 140 ° C. for 7 hours. Thereafter, propionic acid was distilled off, and the resulting black residue was purified with a silica gel column to obtain compound (G).

The instrumental analysis result of the obtained compound (G) was as follows.
¹ H-NMR (300 MHz, CDCl 3) δ (ppm) = 1.49 (s, 18 H), 6.69 (d, J = 4.8 Hz, 2H), 7.01 (d, J = 4.8 Hz, 2H), 7.57 (m, 5H), 7.90 (s, 4H), 8.02 (s, 2H), 8.31 (d, J = 8.1 Hz, 2H), 8.47 (d , J = 8.1Hz, 2H)

Under a nitrogen atmosphere, a mixture of 3 mL of methanol containing 0.045 g of compound (G), 0.040 g of cobalt acetate tetrahydrate, and 3 mL of chloroform was heated to 80 ° C. for 5 hours. Stir. When the obtained solution was concentrated and dried to solidify, a blue solid was obtained. This blue solid was washed with water to obtain a metal complex (H).

The instrumental analysis result of the obtained metal complex (H) was as follows.
ESI-MS [M + ·]: 866.0

The metal complex (H) and the carbon support (Ketjen Black EC600JD, manufactured by Lion) were mixed at a mass ratio of 1: 4, and the resulting mixture was stirred in methanol at room temperature and then at room temperature. Comparative composition (I) was prepared by drying under reduced pressure of 200 Pa for 12 hours.

Next, a comparative modified product (J) was obtained in the same manner as in Example 4 except that the composition (E) was replaced with the comparative composition (I) in Example 4.

<Evaluation>
(Evaluation of oxygen reduction ability by rotating ring disk electrode)
As the electrode, a ring disk electrode in which the disk part is glassy carbon (diameter 4.0 mm) and the ring part is platinum (ring inner diameter 5.0 mm, ring outer diameter 7.0 mm) was used. To a sample bottle containing 2 mg of the composition (E), modified product (F), comparative composition (I) or comparative modified product (J), 0.6 mL of distilled water, 0.4 mL of ethanol and Nafion solution (manufactured by Aldrich, After adding 20 μL of a 5 mass% solution), the mixture was dispersed with ultrasonic waves for 30 minutes. After 4.44 μL of the obtained suspension was dropped onto the disk part of the electrode, the electrode for measurement was produced by drying overnight at room temperature. By rotating the electrode thus produced, the current value of the oxygen reduction reaction at that time was measured. The measurement was performed at room temperature under a nitrogen atmosphere and an oxygen atmosphere. The value obtained by subtracting the current value obtained by the measurement under the nitrogen atmosphere from the current value obtained by the measurement under the oxygen atmosphere is defined as the oxygen reduction current value, and the value obtained by dividing the current value by the disk surface area. The current density was taken. Table 2 shows current density at a potential of 0.4 V (vs RHE (reversible hydrogen electrode)) in an oxygen atmosphere. The measurement apparatus and measurement conditions are as follows.

Measuring device RRDE-2 rotating ring disk electrode device manufactured by BAS Co., Ltd. ALS model 701C dual electrochemical analyzer measurement conditions Cell solution: 0.05 mol / L sulfuric acid aqueous solution (oxygen saturation)
Solution temperature: 25 ° C
Reference electrode: Silver / silver chloride electrode (saturated KCl)
Counter electrode: platinum wire Sweep speed: 5 mV / s
Electrode rotation speed: 2400 rpm

Since the composition (E) prepared in the examples has a higher current density than the comparative composition (I) prepared in the comparative example, the oxygen reducing ability is high.
Since the modified product (F) prepared in the examples has a higher current density than the comparative modified product (J) prepared in the comparative example, the oxygen reducing ability is high.

<Evaluation>
[Solubility test]
1 mg each of the metal complex (D) and the metal complex (H) was taken and placed in a vial, and then 1 ml of water was added and stirred. After 1 hour, the metal complex (D) did not dissolve, but the metal complex (H) partially dissolved, and the water turned light blue.

Therefore, it was found that the metal complex (D) having a linked compound as a ligand has water resistance.

INDUSTRIAL APPLICABILITY Since the present invention can provide an electrode catalyst having a high oxidation-reduction ability, a metal complex and a compound useful for the production thereof, it is extremely useful industrially.

Claims (16)

1. A compound comprising a residue of a compound represented by the following formula (1) and a divalent aromatic group which may have a substituent, wherein the number of the residues is 2 to 4 And a compound in which the number of the divalent aromatic group is 1 to 3, and the sum of the number of the residue and the divalent aromatic group is 3 to 5.
   

   

   [In Formula (1), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a group represented by any of the following formulas:
   

   

   (In the formula, each R ^α independently represents a hydrogen atom or a hydrocarbyl group.)
   P ¹ is an atomic group forming a heterocyclic ring containing Y ¹ ; P ² is an atomic group forming a heterocyclic ring containing Y ² ; P ³ forms a heterocyclic ring containing Y ³ ; P ⁴ is an atomic group forming a heterocyclic ring containing Y ⁴ ; P ⁵ and P ⁶ are each independently an atomic group forming an aromatic ring or a heterocyclic ring; P ¹ , The heterocyclic ring formed by P ² , P ³ and P ⁴ , and the aromatic ring and heterocyclic ring formed by P ⁵ and P ⁶ may each have a substituent; P ¹ and P ² are bonded to each other May form a ring with Q ¹ ; P ² and P ⁶ may be bonded to each other to form a ring; P ⁶ and P ⁴ may be bonded to each other to form a ring well; P ⁴ and P ³ may form a ring together with Q ² to combine with each other; may be the P ³ and P ⁵ are bonded to each other to form a ring; P ⁵ and P ¹ are each other It may bond to form a ring; Q ¹ and Q ² each independently a linking group or a direct bond; Z ¹ and Z ² are, each independently, a hydrogen atom, or, the following formula Represents a group represented by:
   

   

   (Wherein, each represent R ^beta independently a hydrogen atom or a hydrocarbyl group.). ]
2. In the formula (1), the atomic group represented by P ⁵ and Z ¹ are integrated to form a phenol structure, and the atomic group represented by P ⁶ and Z ² are integrated. The compound according to claim 1, which has formed a phenol structure.
3. In the formula (1), the heterocyclic ring formed by P ¹ , the heterocyclic ring formed by P ² , the heterocyclic ring formed by P ³ , and the heterocyclic ring formed by P ⁴ are aromatic heterocyclic rings. 1. The compound according to 1.
4. In the formula (1), the aromatic heterocyclic ring formed by P ¹ , the aromatic heterocyclic ring formed by P ² , the aromatic heterocyclic ring formed by P ³ , and the aromatic heterocyclic ring formed by P ⁴ include The compound according to claim 3 which is a nitrogen aromatic heterocycle.
5. The compound according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (2).
   

   

   [In the formula (2), R ¹ is a hydrogen atom or a monovalent group; a plurality of R ¹ may be the same or different, and R ¹ are bonded to each other to form a ring. Q ³ and Q ⁴ each independently represent a divalent group represented by any of the following formulae:
   

   

   [Wherein R ² represents a hydrogen atom or a monovalent group; a plurality of R ² may be the same or different, and R ² may be bonded to each other to form a ring; X ¹ represents a nitrogen atom or a trivalent group; R ³ represents a hydrogen atom or a monovalent group; a plurality of R ³ may be the same or different, and R ³ are bonded to each other. X ² may represent a group represented by any of the following formulas:
   

   

   (In the formula, R ′ represents a hydrogen atom or a hydrocarbyl group.)
   A plurality of X ² may be the same or different; R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a monovalent group; R ⁴ and R ⁶ are bonded to each other; R ⁵ and R ⁶ may be bonded to each other to form a ring, and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. . ]. ]
6. The compound of Claim 1 represented by following formula (3).
   

   

   [In formula (3), R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent group; a plurality of R ⁷ may be the same or different, and R ⁷ may be mutually different. A plurality of R ⁸ may be the same or different, and R ⁸ may be bonded to each other to form a ring; Q ⁵ is a group represented by the following formula: Represents a divalent group represented by:
   

   

   [Wherein R ⁹ represents a hydrogen atom or a monovalent group; a plurality of R ⁹ may be the same or different, and R ⁹ may be bonded to each other to form a ring. ; X ³ represents a nitrogen atom or a trivalent group; R ¹⁰ represents a hydrogen atom or a monovalent group; plural R ¹⁰ may be different even in the same, R ¹⁰ together are They may combine with each other to form a ring; X ⁴ represents a group represented by any of the following formulae:
   

   

   (In the formula, R ′ represents a hydrogen atom or a hydrocarbyl group.)
   A plurality of X ⁴ may be the same or different; R ¹¹ and R ¹² each independently represents a hydrogen atom or a monovalent group; R ¹¹ and R ¹² are bonded to each other; To form a ring. ]
   A plurality of Q ⁵ may be the same or different; Ar represents a divalent aromatic group which may have a substituent; ]
7. A metal complex having a metal atom or metal ion and a ligand, wherein the ligand is the compound according to claim 1.
8. The metal complex according to claim 7, wherein the metal in the metal atom or metal ion is a transition metal belonging to the fourth to sixth periods of the periodic table.
9. The metal complex according to claim 8, wherein the metal in the metal atom or metal ion is manganese, iron, cobalt, nickel, copper, or platinum.
10. The metal complex according to claim 7, wherein the number of metal atoms or metal ions is 1 to 4.
11. A modified product obtained by heating a mixture comprising the metal complex according to claim 7 and a carbon support.
12. The modified product according to claim 11, wherein the heating temperature is 600 ° C to 1200 ° C.
13. The composition containing following (a) and following (b).
    (A) The metal complex according to claim 7 (b) at least one component selected from the group consisting of a carbon support and a polymer compound
14. The composition containing following (a ') and following (b').
    (A ′) Modified product according to claim 11 (b ′) polymer compound
15. A catalyst comprising the metal complex according to any one of claims 7 to 10, the modified product according to claim 11 or 12, or the composition according to claim 13 or 14.
16. A fuel cell electrode catalyst comprising the catalyst according to claim 15.